CN108473601A - Online blend method - Google Patents
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- CN108473601A CN108473601A CN201680074936.6A CN201680074936A CN108473601A CN 108473601 A CN108473601 A CN 108473601A CN 201680074936 A CN201680074936 A CN 201680074936A CN 108473601 A CN108473601 A CN 108473601A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/06—Organic solvent
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/0064—Feeding of liquid into an evaporator
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/0082—Regulation; Control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/14—Evaporating with heated gases or vapours or liquids in contact with the liquid
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- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
A kind of online blend method for polymer, including：(a) two or more are provided and is in parellel arranged reactor low pressure separator unit (1,7), each reactor low pressure separator unit includes a reactor (2,8) for being fluidly connected to a down stream low pressure separator (3,9) and the low pressure separator (3,9) connection is further back to the recovery line (5,11) of respective reaction device (2,8)；(b) with olefinic monomer of the polymerisation in solution polymerization with two or more carbon atoms in each reactor (2,8)；(c) in each reactor (2, 8) formation includes the unbated reactor effluent stream of homogeneous flow bulk polymer monomer solvent mixture in, (d) make from each reactor (2, 8) the unbated reactor effluent stream passes through corresponding low pressure separator (3, 9), therefore the low pressure separator (3 is had adjusted, 9) temperature and pressure, so that obtaining liquid phase and vapor phase, to generate rich in polymers liquid phase and poor polymer vapor phase, and (e) in each low pressure separator (3, 9) the poor polymer vapor phase is detached from the rich in polymers liquid phase to form the poor polymer vapor stream of separation and the rich in polymers liquid flow of separation in；(f) merge the rich in polymers liquid flow from step (e) in other low pressure separator and/or mixer (13) to generate the rich in polymers liquid flow (16) of merging；(g) the poor polymer vapor stream from step (e) is introduced back into corresponding reactor (2,8) via recovery line (5,11).
Description
Technical field
The present invention relates to the online blend methods for producing the reactor that two parallel deployments of polymer operate.
Background technology
In traditional polymer production, reactor is serial operation.This operation allows to use different technique items
Part, therefore the property of the polymer produced in single reactor can be changed.In a certain range, such as whole objects can be changed
Expect the molecular weight distribution of (material produced in all reactors).However, independently of other step polymer it is independent
Polymerization also needs, because when without the concern for second step or third step, there is more possibility for adjusting micro-structure
Property.For example, if to produce bimodal polyolefin, the material for being transferred to another reactor from a reactor is still activity
, i.e., remaining catalyst activity will determine the selection of second reactor product.Addition is other and optional different catalyst
Still dependence cannot be remedied.
When operating two or more reactors with parallel deployment, blend method is to the uniformity of final blend to closing weight
It wants.It is well known that the blending of the resin with very different molecular weight is fairly limited in the conventional method.In addition to this,
Traditional blend method is unacceptable for liquid polymeric, because temperature is higher than the fusing point of polymer, is automatically led to
Residence time in reactor is very short.In other words, blend method becomes an important factor for space-time yield.
WO2009/035580A1, US2009/163643A1 and US2009/163642A1 disclose some blend methods,
In the homogeneous liquid polymeric blends that polymerize in parallel polymerisation in solution in single or multiple liquid-liquid high-pressure separators point
From.But the shortcomings that these methods, is：Polymer concentration in rich in polymers liquid flow is at a fairly low, it is therefore desirable to additional
Downstream separator obtains straight polymer.In addition, due to the high pressure for being generally at least 5MPa in separation process, it may occur however that no
Desired reactor downstream polymerization, this usually requires to kill polymerization catalyst with polar substances.The catalyst agent for killing makes
MONOMER RECOVERY from poor polymer flow complicates.
Invention content
The present invention is based on following discoveries：When each reactor independently with further include only connecting reactor and low pressure separator
Recovery line low pressure separator connection when, the shortcomings that blend method of the prior art can be overcome.
The present invention there is provided herein a kind of online blend method for polymer, including：
(a) two or more are provided and is in parellel arranged reactor-low pressure separator unit (1,7), it is each to react
Device-low pressure separator unit include a reactor (2,8) for being fluidly connected to a down stream low pressure separator (3,9) and into
The recovery line (5,11) that the low pressure separator (3,9) connection is back to respective reaction device (2,8) of one step；
(b) it is listed in the two or more reactors of each reactor-low pressure separator unit (1,7) and connects under making
It touches：
1) olefinic monomer with two or more carbon atoms,
2) one or more catalyst systems,
3) optional one or more comonomers,
4) optional one or more chain-transferring agents, and
5) optional one or more diluents or solvent,
The wherein described reactor (2,8) operates in the case where ensuring operating condition that reactor content forms single homogeneous phase,
The reactor content includes the olefinic monomer, any existing comonomer, any existing diluent or solvent, appoints
What existing chain-transferring agent and polymeric articles；
The catalyst system for being accordingly used in each reactor includes one or more catalyst precarsors, one or more
Activator and optional one or more catalyst carriers；
(c) it includes homogeneous flow bulk polymer-monomer-solvent mixture to be formed in each reactor (2,8)
Unbated reactor effluent stream,
(d) the unbated reactor effluent stream from each reactor (2,8) is made to pass through corresponding low
Separator (3,9) is pressed,
Therefore the temperature and pressure of the low pressure separator (3,9) is had adjusted so that liquid phase and vapor phase are obtained, to
Rich in polymers liquid phase and poor polymer vapor phase are generated, and
(e) in each low pressure separator (3,9) by the poor polymer vapor phase from the rich in polymers liquid
Separation is to form the poor polymer vapor stream of separation and the rich in polymers liquid flow of separation in phase；
(f) merge the rich in polymers liquid from step (e) in other low pressure separator and/or mixer (13)
Body stream is to generate the rich in polymers liquid flow (16) of merging；
(g) the poor polymer vapor stream from step (e) is introduced back into corresponding via recovery line (5,11)
Reactor (2,8) in.
Online blend method for polymer is related to optionally having two or more intermediates of different nature polymerization
Object is continuously mixed to obtain final polymer.Online blend method is opposite with traditional blend method in batches.In blending side in batches
In method, final products are in blender by merging the different intermediate products from storage tank.
Reactor-low pressure separator unit includes reactor and low pressure separator and connecting pipeline.In simplest reality
It applies in mode, only there are one reactors.However, it is possible to there are two or multiple coupled in series reactor, although this is not usually
Preferably.
Reactor according to the present invention can be suitable for that any reactor being polymerize can be operated in a continuous mode.
Such reactor is well known in the art.Apart from the others, suitable example is the autoclave operated in a continuous mode
Or stirred tank reactor or tubular reactor.
Corresponding reactor indicates that first reactor is only connected to the first low pressure separator, and second reactor is only connected to
Second low pressure separator.
Low pressure separator indicates the unit for the separation of volatile components from relatively dilute polymer solution.Volatility group
Divide and usually exists with the amount of by weight about 10% to about 90% of solution.In low pressure separator, liquid phase is (comprising being dissolved in
Polymer therein) and vapor phase coexist.Preferably, low pressure separator is at up to 20 bars, such as 1 bar to 15 bars (absolute pressure
Power), it operates under the pressure of preferably 2 bars to 12 bars (absolute pressure).Low pressure separator is all known in decades.The shape of two-phase
At bringing rich in polymers liquid phase and poor polymer vapor phase.Containing unreacted monomer, solvent and traces of polymer and again
The poor polymer vapor phase of comonomer (if present) has 100kg/m3Or lower density.
Low pressure separator and separation (the wherein polymer-rich phase and poor polymer under lower critical solution temperature (LCST)
All it is substantially mutually liquid or supercritical fluid) it is opposite.
The low pressure separator of reactor is connected in downstream fluid means that low pressure separator is arranged such that receive
Collect the reaction mixture generated in the reactor.Connection be typically simply one pipe, be optionally equipped be useful for control and/or
The device of transport and/or heating.
The recovery line of connection reactor according to the present invention and corresponding low pressure separator allows the one or more of separation
Monomer feed Returning reactor.
Recovery line according to the present invention only connects the reactor and low pressure point for all forming reactor-low pressure separator unit
From device.For example, if there is the first reactor including reactor A and low pressure separator A '-low pressure separator unit and packet
Reactor B and second reactor-low pressure separator unit of low pressure separator B ' are included, then there is only reactor As detaches with low pressure
Recovery line between recovery line and reactor B between device A ' and low pressure separator B '.Reactor A and low pressure separator
Connection between B ' is forbidden.
Catalyst according to the invention system indicates catalyst or catalyst precarsor, co-catalyst (if present), activation
Agent (if present), catalyst carrier (if present) and existing external electron donor.
Chain-transferring agent is can to pass through chain-transferring agent, the polymer chain of growth with the substance of the polymer chain reaction of growth
Activity be transferred.Most common chain-transferring agent is hydrogen in polyolefin polymerization.Chain transfer reaction reduces final polymer
Average molecular weight.
Polymerization system in its dense fluid state means that the polymerization is polymerisation in solution.This means that one or more
Monomer and the one or more comonomers being optionally present are dissolved in the non-reactive solvent containing catalyst system.Polymerization production
The raw polymer being also dissolved in selected solvent.
Unbated reactor effluent stream according to the present invention be directed to reactor, not through it is any processing lead
Cause the effluent stream of concentration variation.
Homogeneous flow bulk polymer-monomer-solvent mixture indicates that there is no phase separations.
It must be relative to the unbated reactor effluent for including homogeneous flow bulk polymer-monomer-solvent mixture
To understand polymer-rich phase.If the amount of polymers relative to total mixture is higher than poly- in unbated reactor effluent stream
Object amount is closed, then this is mutually rich in polymers.
Polymer-poor phase is generated when unbated reactor effluent stream is divided into polymer-rich phase and polymer-poor phase.
Polymer-poor phase indicates there is the polymer lower than the polymer content of unbated reactor effluent stream relative to mixture
Any phase of content.Poor polymerization containing unreacted monomer, solvent and traces of polymer and weight comonomer (if present)
Object mutually has 100kg/m3Or lower density.
The poor polymer vapor phase of term is mutually indicated with rich in polymers liquid：In the present invention, polymer-poor phase is vapor phase
And polymer-rich phase is liquid phase.
The poor polymer vapor phase of term and rich in polymers liquid are mutually also it is understood that indicate a kind of relationship.When with poor polymer
When vapor phase is compared, rich in polymers liquid mutually has higher polymer content.When the process for considering to occur in low pressure separator
When, what this will be appreciated that：Make the unbated reactor effluent from each reactor (2,8) across corresponding low pressure point
From device (3,9) and the temperature and pressure of low pressure separator is adjusted, generates liquid phase and vapor phase.Technical staff will be understood that, steam
Air-flow can contain a small amount of liquid (by volume), for example, drop and polymer beads.Those skilled in the art will also manage
Solution, liquid flow can contain a small amount of steam, such as vapour bubble.
Specific implementation mode
Fig. 1 shows the configuration of two reactors-low pressure separator unit, and it includes first reactor low pressure separator lists
Member 1, the first reactor low pressure separator unit 1 include：First reactor 2 and the first low pressure separator 3；Connection first is anti-
The first connecting pipeline 4 of device 2 and the first low pressure separator 3 is answered, the transmission of the first connecting pipeline 4 includes homogeneous fluid phase-polymerization
The unbated reactor effluent stream of object-monomer-solvent mixture；It connects the first low pressure separator 3 and is back to the first reaction
First recovery line 5 of device 2；Heat the primary heater 6 of unbated reactor effluent stream.
Second reactor low pressure separator unit 7 includes：Second reactor 8 and the second low pressure separator 9；Connection second is anti-
It includes that homogeneous fluid is met to answer the second connecting pipeline 10 of device 8 and the second low pressure separator 9, the transmission of the second connecting pipeline 10
Close the unbated reactor effluent stream of object-monomer-solvent mixture；It connects the second low pressure separator 9 and returns to the second reaction
Second recovery line 11 of device 8；Heat the secondary heater 12 of unbated reactor effluent stream.
Third low pressure separator and/or mixer 13 can be connected by third connecting pipeline 14 and the 4th connecting pipeline 15,
The third connecting pipeline 14 connects the first low pressure separator 3 and third low pressure separator 13, and the third connecting pipeline 14 passes
Send the rich in polymers liquid flow extracted from the first low pressure separator 3；4th connecting pipeline 15 connects the separation of the second low pressure
Device 9 and third low pressure separator 13, the 4th connecting pipeline 15 transmit the polymer-rich phase extracted from the first low pressure separator 9
Liquid flow.
The rich in polymers liquid flow of merging is taken out from third low pressure separator and/or mixer 13 via pipeline 16.
In the online blend method of polymer according to the present invention, at least two reactors-low pressure separator list is used
Member 1,7, therefore each reactor-low pressure separator unit includes that a reactor 2,8 and one are fluidly connected to reactor
2, the low pressure separator 3,9 in 8 downstreams, and the further recovery line 5,11 for only connecting reactor and low pressure separator.Instead
Device 2,8 and low pressure separator 3,9 is answered to be fed to via the unbated reactor effluent of connection permission of connecting pipeline 4,10 low
It presses in separator 3,9.It is of course possible to operate three, four or even more reactor-low pressure point with this parallel deployment
From device unit.The rich in polymers liquid flow taken out from all low pressure separators of reactor-low pressure separator unit all exists
Merge in down stream low pressure separator and/or mixer 13 to generate the rich in polymers liquid flow of merging, the rich polymerization of the merging
Thing liquid body, which is flowed through, to be taken out by pipeline 16 from low pressure separator and/or mixer 13.
Polymerization
In the reactor, using with two or more carbon atoms olefinic monomer, one or more catalyst systems, appoint
One or more comonomers of choosing, optional one or more chain-transferring agents and optional one or more diluents or molten
Agent causes liquid polymeric.Therefore, the polymerization system of each reactor is in its dense fluid state and includes olefinic monomer, appoints
What existing comonomer, any existing diluent or solvent, any existing chain-transferring agent and polymer product.
Self-explaining to be, when comparing each other, the reaction condition applied in different reactor need not be the same, but
Different.This allows the different polymer that production is finally blended together.Due to reaction condition may be completely independent of it is other
One or more reactors are adjusted, so the option for changing the microstructure for the polymer to be blended is very wide in range.For example,
The charging etc. of catalyst system, pressure, temperature, monomer feed, comonomer/monomer ratio, chain-transferring agent can be different.
There are countless possibility.
The reactor being used in the present invention is preferably selected from by tubular reactor, agitated autoclave, tank reactor, circulation
The group of reactor or combination thereof composition.
Olefinic monomer is the alpha-olefin with two or more carbon atoms, preferably 2 to 10 carbon atoms.Suitable α-alkene
Hydrocarbon monomer selects the group of free ethylene, propylene, 1- butylene, 1- hexenes, 1- octenes, 1- decene and styrene composition.It is highly preferred that alkene
Hydrocarbon monomer selects the group of free ethylene, propylene and 1- butylene composition.Particularly preferred olefinic monomer is ethylene or propylene.
One or more comonomers are optionally and preferably present at least one polymer reactor.Comonomer be selected from by
The alpha-olefin different from the olefinic monomer with 2 to 12 carbon atoms；Polyenoid, for example, it is non-with 4 to 12 carbon atoms
It is conjugated α-ω-diene, the group that the cycloolefin with 6 to 20 carbon atoms and the Cyclic Polyene with 6 to 20 carbon atoms form.
Preferably, when olefinic monomer is ethylene, comonomer is selected from α-alkene different from olefinic monomer with 2 to 12 carbon atoms
The group of hydrocarbon, such as 1- butylene, 1- hexenes and 1- octenes；When olefinic monomer is propylene, comonomer be selected from ethylene, 1- butylene and
1- hexenes.
Suitably, comonomer is present in two polymer reactors.It can be used in two polymer reactors same
Comonomer, but if necessary to (such as according to product characteristics), they can also be different.In addition, in two reactors
The concentration of one or more comonomers is suitably different from each other.This allows the homogeneous blend of the different polymer of two kinds of production
Object.Make the concentration of one or more comonomers in two reactors identical however, it is also possible to operate reactor.
Polymerization catalyst can be any catalyst known in the art for capableing of polymerized monomer and optional comonomer.
Therefore, polymerization catalyst can be such as the Ziegler-disclosed in EP-A-280352, EP-A-280353 and EP-A-286148
Natta catalyst or it can be such as WO-A-1993025590, US-A-5001205, WO-A-1987003604 and US-A-
Metalloscene catalyst disclosed in 5001244 or it can be these combination.Other suitable catalysis can also be used
Agent, such as late transition metal catalyst.
As known in the art, chain-transferring agent can be used in one or two polymer reactor to control the molecule of polymer
Amount.For example, suitable chain-transferring agent is hydrogen.By keeping the chain-transferring agent of various concentration, Ke Yisheng in two reactors
Produce the blend polymer with widened molecular weight distribution.
Solvent is suitably present in polymerization process.Solvent can any suitable have the straight of 3 to 20 carbon atoms
Chain or branched alkyl, the optional cyclic alkyl with alkyl substituent with 5 to 20 carbon atoms, or there are 6 to 20 carbon
The mixture of the aryl or two or more compounds listed optionally with alkyl substituent of atom.Solvent must
It must be inert to polymerization catalyst and monomer.In addition, it should stablize under polymerization conditions.In addition it must also be able to polymerizeing
Under the conditions of dissolving monomer, possible comonomer, possible chain-transferring agent and polymer.
Temperature in reactor makes the polymer formed in the polymerization be dissolved completely in comprising solvent, one kind or more
In the reaction mixture of kind comonomer, chain-transferring agent and polymer.Temperature is suitably more than the fusion temperature of polymer.Cause
This depends on the content of comonomer unit in the polymer when polymer is the homopolymer or copolymer of ethylene, and temperature is closed
It it is suitable 120 DEG C to 240 DEG C, such as 140 DEG C to 220 DEG C, most preferably 150 DEG C to 200 DEG C.When the homopolymer that polymer is propylene
Or when copolymer, the content of comonomer unit in the polymer is depended on, temperature is suitably 120 DEG C to 250 DEG C, such as
140 DEG C to 235 DEG C, most preferably 150 DEG C to 225 DEG C.
On the one hand pressure in reactor depends on temperature, on the other hand depend on the type and amount of comonomer.Pressure
It is suitably for 50 bars to 300 bars, preferably 60 bars to 250 bars and 70 bars to 200 bars more preferable.
This method is suitably continuous operation.Therefore, monomer, catalyst stream and comonomer, chain tra nsfer when it is present
Agent and solvent stream are sent in one or more reactors 2,8.It is (such as unbated that product stream is taken out from reactor 2,8
Reactor effluent stream), the product stream include unreacted monomer, the polymer of dissolving and optional unreacted comonomer and
Chain-transferring agent and optional solvent.
A polymerization homopolymer or random copolymer in two or more reactors 2,8 in a preferred aspect, and
A polymerized copolymers at least two or more reactors.This allows to change point of comonomer in final polymer
Cloth.For example, if purpose is to introduce comonomer to specified molecular weight range, one in reactor 2,8 can be operated, is made
It obtains close to the specified molecular weight and uses comonomer.In parallel reactor, comonomer can not be used, and can
With regularization condition so that avoiding the specified molecular weight range obtained in parallel reaction device substantially.Homopolymer is preferably selected from
Rule found structure polypropylene, syndiotactic polypropylenes, atactic polypropylene, polyethylene, polybutene, polybutadiene, polypenthylene, gather oneself
Alkene, poly- heptene, polyoctenamer, poly decene and polystyrene.
When producing copolymer, it is preferably selected from ethylene-propylene copolymer ,-1 copolymer of propene-1-butene, propylene pentene-1-1
Copolymer, -1 copolymer of butene-hexene, -1 copolymer of propylene-heptene, -1 copolymer of propylene-octene, propylene-decene -1 are copolymerized
Object, -1 copolymer of Ethylene/Butylene, -1 copolymer of ethylene-pentene, -1 copolymer of polyethylene-hexene, -1 copolymer of ethylene-heptene, second
Alkene-octene-1 copolymer and their mixture.If second polymer to be blended is homopolymer or random copolymer,
Then this copolymer is especially significant.Preferably, merge one or more polymer.
Preferred process conditions are at preferably at least 120 DEG C, more preferably at least 140 DEG C and most preferably at least in reactor
At a temperature of 150 DEG C and preferably at least 5.0MPa, more preferably at least 6.0MPa and most preferably at least 7.0MPa pressure
Under.
In the method according to the invention, the volume ratio of at least two reactors relative to each other preferably in 0.85/1.0 and
1.0/0.85 interior.
Polymerization cause after, from reactor 2,8 taking-up include homogeneous flow bulk polymer-monomer-solvent mixture not
The reactor effluent stream of reduction.The step is carried out for any existing reactor-low pressure separator, i.e., matches simplest
The step is carried out twice in setting.
Based on the total weight content of unbated reactor effluent stream, unbated reactor effluent stream preferably comprises
By weight 10% to 35% polymer, further preferably by weight 12% to 30% polymer, most preferably by weight
The polymer of meter 15% to 25%.
Heating
Future autoreactor 2,8 unbated reactor effluent flow into and expect low pressure separator 3,9 before, usually
In at least one heating stepses, the stream is preferably preheated in two heating periods (including warm-up phase and final heating period).
Typically, it when polymer is the homopolymer or copolymer of ethylene, before entering the first heating stepses, does not reduce
Reactor effluent stream temperature be 120 DEG C to 240 DEG C, preferably 140 DEG C to 220 DEG C, most preferably 150 DEG C to 200 DEG C.It is typical
Ground, when polymer is the homopolymer or copolymer of propylene, before entering the first heating stepses, unbated reactor outflow
The temperature of logistics is 120 DEG C to 250 DEG C, preferably 140 DEG C to 235 DEG C, most preferably 150 DEG C to 225 DEG C.
When polymer is the homopolymer or copolymer of ethylene, the immediately unbated reactor outflow in preheating step downstream
The temperature of logistics is usually 160 DEG C to 240 DEG C and preferably 170 DEG C to 220 DEG C, most preferably 180 DEG C to 200 DEG C.Work as polymer
When being the homopolymer or copolymer of propylene, immediately the temperature of the unbated reactor effluent stream in preheating step downstream is usually
200 DEG C to 250 DEG C, preferably 210 DEG C to 250 DEG C, most preferably 220 DEG C to 250 DEG C.
It is preferred that the pressure of unbated reactor effluent stream is not influenced substantially by preheating step.Pressure is suitably 50
It is bar to 300 bars, preferably 50 bars to 250 bars and 70 bars to 200 bars more preferable.
Unbated reactor effluent stream is transmitted to the first heating stepses from reactor 2,8.First heating stepses
Purpose is that the first unbated reactor effluent stream is preheated before entering separating step.
Preheating is usually carried out by heat exchanger 6,12.For example, unbated reactor effluent flow distribution is in multiple pipes
In, and heating fluid is passed through with contacting pipe, to heat the solution wherein flowed.
The purpose of preheating step is to recycle heat from technique stream, so as to improve the economy of technique.
It can be any process fluid for including heat-recoverable to heat fluid.It is preferred that poor poly- by what is recycled from separating step
It closes object vapor stream and is used as heating fluid.In the process, heating fluid (such as poor polymer vapor stream) is cooled.It is preferred that from poor
So many heat is extracted in polymer vapor stream makes the poor polymer vapor stream of at least part cold in the first heating stepses
It is solidifying.
The configuration of the present invention makes it possible to shift and be used advantageously in the heat obtained in low pressure separator 3,9.Therefore,
In a preferred embodiment, preheating is completed by heat exchanger 6,12, which will come from low pressure separator
The waste heat of separation is transferred on unbated reactor effluent stream.
It is preheated when by heat exchanger 6,12, which will come from poor polymer vapor stream (from low pressure
Extracted in separator 3,9) heat be transferred to unbated reactor effluent stream (come from two or more reactors 2,8)
When upper, cooling poor polymer vapor stream at least partly condenses preferably in heat exchanger 6,12.
Preferably, preheating is carried out by heat exchanger, which is transferred to the heat of the separation from step (d)
On unbated reactor effluent from two or more reactors, therefore what is cooled down in a heat exchanger flow to few portion
Divide ground condensation.
When the unbated reactor effluent stream from two or more reactors 2,8 is including warm-up phase and most
When being heated in two stages of whole heating period, the preferably final heating period includes that stream is heated at least 200 DEG C.
Preferably, the final heating period include by unbated reactor effluent stream be heated to preferably at least 180 DEG C, more
Preferably at least 200 DEG C and most preferably at least 210 DEG C.
The purpose of final heating stepses is the temperature being heated to unbated reactor effluent stream needed for separating step.
Final heating stepses may be needed, because the heat-recoverable in preheating step in heat medium may be not enough to reach do not subtract
The preferred temperature of few reactor effluent stream.
Final heating stepses can be carried out by using principle similar with preheating step.However, final heating stepses
The temperature of the middle heating fluid used, which is suitably controlled to the unbated reactor effluent stream of permission, is heated to preferred temperature
Temperature.It is preferred, therefore, that before the heating fluid stream that will be used in final heating stepses introduces final heating stepses,
Fluid flows heat will be heated to desired temperature.
According to embodiment of the present invention, in the unbated reactor effluent stream of the measured downstream of preheating step
Temperature, and finally added to adjust based on the difference between the measuring temperature and preferred temperature of unbated reactor effluent stream
The flow of the heating fluid used in hot step.
When polymer is the homopolymer or copolymer of ethylene, the unbated reactor outflow in final heating stepses downstream
The temperature of logistics is usually 200 DEG C to 300 DEG C, preferably 210 DEG C to 260 DEG C and 210 DEG C to 230 DEG C more preferable.Work as polymer
For propylene homopolymer or copolymer when, the temperature of the unbated reactor effluent stream in final heating stepses downstream is usually
200 DEG C to 300 DEG C, preferably 210 DEG C to 270 DEG C and 220 DEG C to 250 DEG C more preferable.
It is preferred that the pressure of unbated reactor effluent stream is not influenced substantially by final heating stepses.Pressure is suitable
Ground is for 50 bars to 300 bars, preferably 50 bars to 250 bars and 70 bars to 200 bars more preferable.
Separation
The unbated reactor effluent stream for carrying out autoreactor 2,8 is fed to and distributes to the low of the reactor 2,8
It presses in separator 3,9, to form reactor-low pressure separator unit 1,7.In low pressure separator unit 1,7, by adjustment temperature
Degree and pressure are to obtain liquid phase and vapor phase.Polymer is dissolved in liquid phase, which includes mutually the possible solvent in part
With the possible unreacted comonomer in part, and most of unreacted monomer, possible unreacted chain transfer agent, possible part
Unreacted comonomer and possible partial solvent form vapor phase.
When polymer is the homopolymer or copolymer of ethylene, the temperature in separating step is suitably at 120 DEG C to 240
DEG C, preferably 140 DEG C to 220 DEG C and it is 150 DEG C to 200 DEG C more preferable in the range of.When polymer is the homopolymer of propylene or is total to
When polymers, temperature in separating step suitably at 120 DEG C to 240 DEG C, preferably 140 DEG C to 220 DEG C and it is more preferable 150 DEG C extremely
In the range of 200 DEG C.
Pressure in separating step is for 1 bar to 15 bars, preferably 2 bars to 12 bars and 5 bars to 10 bars more preferable.
Condition in separating step should make reactor downstream will not occur it is unwanted polymerization (this usually requires to use pole
Property substance kill polymerization catalyst).Therefore, in the preferred aspect of the present invention, for before the step of separating or period, not to not
Catalyst agent for killing is added in the reactor effluent stream of reduction.
In another aspect of this invention, however, it is not preferred, for before the step of separating or period kills catalyst
Agent is added in unbated reactor effluent stream.Catalyst agent for killing is typically polar compound, as water, alcohol (such as methanol and
Ethyl alcohol), odium stearate/calcium, CO and combination thereof.
As described above, the condition in separating step is it is required that form vapor phase and liquid phase.Therefore reactant to react
Recycling in device can be maintained as simply as possible.
Therefore, polymer-rich phase and polymer-poor phase are obtained.Temperature and pressure is set so that vapor-liquid occurs
It detaches and generates the binary system comprising rich in polymers liquid phase and poor polymer vapor phase.Then the two mutually divide each other
From.
Then in each low pressure separator, poor polymer vapor phase is detached from rich in polymers liquid phase to form separation
Poor polymer vapor stream and rich in polymers liquid flow.
Separating step can be carried out according to any separation method that wherein liquid phase known in the art and vapor phase coexist.
It is easy due to operating, is preferably carried out separating step as flash steps.As known in the art, liquid feedstock is transmitted
Into the container operated under reduced pressure.Therefore a part of liquid mutually evaporates and can be from flash distillation as top stream (or steam
Stream) it takes out.Then it is taken out remaining part in liquid phase as bottom stream (or liquid flow).
There are the advantages of vapor phase and liquid phase it is that device is simple, therefore cost of investment is low first in separating step.This
Outside, the polymer carried in vapor stream is minimum.The rich in polymers liquid flow of concentration is taken out from the liquid phase of separating step.
In preferred embodiments, the flash steps that separating step is discussed further below.Flash steps are suitably flashing
It is carried out in device, which is the vertical container for preferably having generally cylindrical shape.Therefore, flash vessel has roughly circular cross
The part in section.Preferably, there is flash vessel column part, the column part to have cylindrical shape.In addition to cylindrical portion divides it
Outside, the flash vessel can also have extention, such as can be cone bottom part and can be hemispheric top
Part.Alternatively, flash vessel can also have conical shaped shape.
Temperature in flash vessel is usually 120 DEG C to 240 DEG C.Temperature should be high enough that the viscosity of liquid flow is maintained at
It is suitable horizontal, but less than the degradation temperature of polymer.Pressure in flash vessel is usually 15 bars to atmospheric pressure, or even lower than
Atmospheric pressure.
Unbated reactor effluent stream enters flash vessel at top.Liquid flow travels downwardly in flash vessel, and from
The gas evaporated in liquid flow travels upwardly.According to the preferred embodiment, liquid flow is formed in flash vessel and falls downwards
Film.This is conducive to remove dealkylation from liquid flow.The vapor stream usually formed from the gas of evaporation is from the top of flash vessel
It takes out, and liquid flow is taken out from bottom.
According to a particularly preferred embodiment, unbated reactor effluent stream is sprayed in flash vessel.Spray
Mist can be completed by using the suitable nozzle of one or more that unbated reactor effluent stream is dispersed into drop.
This nozzle be industrially it is known, including air atomizer spray nozzle, flat fan nozzles, hollow cone nozzles and full cone spray
Mouth.Preferably, stream is divided into the drop that size is no more than about 1mm by nozzle.
Nozzle forms drop stream in flash vessel.Then drop stream is condensed and is formed with relative high surface in flash vessel
Long-pending falling liquid film.Which enhance the mass transfers of the volatile component from solution.
As described above, flash vessel can have vertical generally cylindrical shape.Then, pass through the suitable position liquid of nozzle
Drip is orientated the tangential of the wall of flash vessel.Therefore, nozzle is suitably located at the position of relatively close wall so that is determined its outlet
To being tangent with wall.When drop stream leaves nozzle, it is moved along the direction of wall, forms downward falling liquid film.Flash vessel also may be used
With with vertical conical shaped shape.In such an embodiment, as set forth above, it is possible to which drop stream to be orientated and dodge
The wall of steaming device is tangent.But it is also possible to which drop to be axially directed to the wall of flash vessel.Then prejudicially by one or more nozzles
It is arranged in flash vessel.In both arrangements, polymer solution forms falling liquid film in flash vessel.
Total weight content based on rich in polymers liquid flow, the polymerization from the rich in polymers liquid flow that flash stage is taken out
Object content be usually by weight 40% to 90%, preferably by weight 50% to 80% and most preferably by weight 60% to
75%.In other words, the total weight content based on rich in polymers liquid flow, from the rich in polymers liquid flow that flash stage is taken out
Usually contain by weight 10% to 60%, preferably by weight 20% to 50% and most preferably by weight 25% to 40%
Residual hydrocarbon.
When seeing from different perspectives, from the poor polymer vapor stream taken out in flash vessel relative to being extracted from flash vessel
Whole material streams are by weight 35% to 80%.Poor polymer vapor stream generally comprises unreacted monomer and solvent and not anti-
Answer comonomer.
By using flash distillation as described above, high separating efficiency may be implemented.For example, for the hydrocarbon containing 6 carbon atoms
Separative efficiency be at least 75%, preferably at least 80%.In addition, being at least for the separative efficiency of the hydrocarbon containing 8 carbon atoms
60%, preferably at least 65%.Separative efficiency is defined as：In equilibrium conditions, the mass flow for the component taken out in vapor stream
Divided by (theory) mass flow of the component in vapor stream.
Preferred process conditions are in low pressure separator：In preferably smaller than 1.5MPa, more preferably less than 1.2MPa and optimal
Under pressure of the choosing less than 1.0MPa, and in preferably smaller than 240 DEG C, more preferably less than 220 DEG C and more preferably less than 200 DEG C of temperature
Under degree.
Rich in polymers liquid flow from low pressure separator 3,9 is total in other low pressure separator and/or mixer 13
It mixes.
Rich in polymers liquid flow is heated before the merging, among merging or after merging in a preferred aspect,.
Above-mentioned separative efficiency of the other low pressure separator usually only in low pressure separator 3,9 is insufficient (i.e. from low pressure point
Content from the residual hydrocarbon in the rich in polymers liquid flow taken out in device 3,9 is quite high) when use.
When rich in polymers liquid flow is blended (i.e. actually substantially only by polymer using other low pressure separator 13
The stream of composition) when, thus obtained other poor polymer vapor phase can be back to any as poor polymer vapor stream
Or in total reactor.This merging of reaction stream is typically harmless, because of the rich polymerization before entering final mix stages
The content of monomer of object liquid flow is very low.In low pressure separator in optional separating step, maintain temperature and pressure with
Form the vapor-liquid binary system of the poor polymer vapor phase comprising combined rich in polymers liquid phase and merging.In addition
Low pressure separator 13 in the poor polymer vapor phase of merging detached from combined rich in polymers liquid phase merged with being formed
Rich in polymers liquid flow and separation merging poor polymer vapor stream.The poor polymer vapor stream of merging is back to instead
It answers in device 2,8, unbated reactor effluent is originated from each in existing two or more reactors.Optionally, divide
From the poor polymer vapor stream of merging be recycled in one or more reactors.
When using mixer 13 come when rich in polymers liquid flow is blended, mixer suitably static mixer.Static state is mixed
Clutch is well known in the present art, and those skilled in the art can be the suitable mixer of the process choice.On the one hand,
The use of mixer enhances the mixing of rich in polymers liquid flow, on the other hand increases volatilization by dramatically increasing mass transfer area
Property component is from liquid mutually to the mass transfer of vapor phase.
Additive can be added into the polymer solution of 13 upstream of low pressure separator and/or mixer, such as anti-oxidant
Agent, processing stabilizers, UV- stabilizers, antitack agent and acid scavenger.Such arrangement allows additive being evenly dispersed in poly-
It closes in object.
It is further preferred that the method for the present invention includes the following steps：From step (d) (i.e. in low pressure separator) and/or step
Suddenly in the poor polymer vapor phase of the separation of (f) (stage being finally blended, be other low pressure separator and/or mixer)
Remove low-molecular-weight oligomer, low-molecular weight polymer, solvents/diluents or combination thereof.For this purpose, mixer
The combination for the other low pressure separator then arranged is preferred.
Vapor stream recycles
The poor polymer vapor stream obtained in low pressure separator 3,9, which is recovered, to be back in corresponding reactor (2,8), not
The reactor effluent stream of reduction is originated from corresponding reactor (2,8).For this purpose, using recovery line 5 and 11.
As explained about reactor-low pressure separator unit, the separation of stream is advantageous.Therefore, it is anti-to be originated from first
The poor polymer vapor stream of device is answered to be back to first reactor, and the poor polymer vapor stream from second reactor recycles back
To second reactor.Recycling itself reduces burning, and be further reduced costs due to less raw materials consumption.
In separating step, vapor stream is taken out from vapor phase.Preferably, by steam be streamed to polymer reactor it
Heat in preceding recycling vapor stream.Preferably, it is molten for heating to be sent to the first heating stepses at least part of vapor stream
Liquid stream.Each existing reactor is done so.Not by poor polymer vapor stream be back to parallel work-flow other
One of reactor.In other words, stringent recycling rule avoids any harmful of the polymerizing condition used in different reactor
Interaction.
In the first heating stepses, the heat carried by vapor stream is transferred in unbated reactor effluent stream.
First heating stepses preferably carry out in heat exchanger 6,12, and heat is transferred to unbated reactor in the heat exchanger
Effluent stream and therefore cooled vapor stream.The degree of part of it condensation can be flowed to cooled vapor.
Then vapor stream is optionally sent into condensing steps.In condensing steps, vapor phase is partially condensed to form condensation
Vapor stream and uncooled vapor stream.When a kind of concentration (being typically the concentration of chain-transferring agent (such as hydrogen)) of component in vapor stream
When higher than concentration in polymer reactor, condensing steps are useful.Then in condensing steps by hydrogen from condensation vapor stream
In separate.It may also be further, it is preferred that vapor stream be condensed in the first heating stepses.It therefore need not be independent
Condensing steps, but the first heating stepses be used as condensing steps.
Then the vapor stream of partial condensation can be separated into condensation vapor stream and uncooled vapor stream.For example, this can be with
It completes in a reservoir.The steam of partial condensation is streamed in container, condensation portion remains liquid in this embodiment, and
Uncooled part remains steam.Then the vapor stream of condensation is taken out from liquid phase, and by uncooled vapor stream from steaming
It is taken out in gas phase.
The vapor stream of condensation is only returned to react with it in the consistent polymer reactor 2,8 of device-low pressure separative element 1,7.
Uncooled vapor stream containing excess component (such as excess hydrogen) is discharged.It is free of and appoints in uncooled vapor stream
In the case that is more than the component of its concentration in polymer reactor 2,8, uncooled vapor stream is reintroduced into reaction
In device 2,8.
In not preferred embodiment, reactor downstream is prevented not as described above by addition catalyst agent for killing
Desired polymerization, the catalyst agent for killing must be removed from poor polymer vapor stream (for example, being absorbed by using fixed bed
Agent or by being removed with alkyl aluminum).
Following clause will summarize the importance of the present invention.
1. a kind of online blend method for polymer, including：
(a) two or more are provided and is in parellel arranged reactor-low pressure separator unit (1,7), it is each to react
Device-low pressure separator unit include a reactor (2,8) for being fluidly connected to a down stream low pressure separator (3,9) and into
The recovery line (5,11) that the low pressure separator (3,9) connection is back to respective reaction device (2,8) of one step；
(b) it is listed in the two or more reactors of each reactor-low pressure separator unit (1,7) and connects under making
It touches：
1) olefinic monomer with two or more carbon atoms,
2) one or more catalyst systems,
3) optional one or more comonomers,
4) optional one or more chain-transferring agents, and
5) optional one or more diluents or solvent,
The wherein described reactor (2,8) operates in the case where ensuring operating condition that reactor content forms single homogeneous phase,
The reactor content includes the olefinic monomer, any existing comonomer, any existing diluent or solvent, appoints
What existing chain-transferring agent and polymeric articles；
Include accordingly one or more catalyst precarsors for the catalyst system of each reactor, one or more
Activator and optional one or more catalyst carriers；
(c) it includes homogeneous flow bulk polymer-monomer-solvent mixture to be formed in each reactor (2,8)
Unbated reactor effluent stream,
(d) the unbated reactor effluent from each reactor (2,8) is made to be detached across corresponding low pressure
Device (3,9),
Therefore the temperature and pressure of the low pressure separator is had adjusted so that liquid phase and vapor phase are obtained, to generate
Rich in polymers liquid phase and poor polymer vapor phase, and
(e) in each low pressure separator (3,9) by the poor polymer vapor phase from the rich in polymers liquid
Separation is to form the poor polymeric liquid stream of separation and the rich in polymers vapor stream of separation in phase；
(f) merge the rich in polymers liquid from step (e) in other low pressure separator and/or mixer (13)
Body stream is to generate the rich in polymers liquid flow (16) of merging；
(g) the poor polymer vapor stream from step (e) is introduced back into corresponding via recovery line (5,11)
Reactor (2,8) in.
2. according to the method described in clause 1 comprising the step of the unbated reactor effluent stream of heating (c)
Suddenly.
3. according to the method described in clause 2 comprising heat the unbated reactor stream of (c) in two stages
The step of effluent stream, described two stages include warm-up phase and final heating period.
4. according to the method described in clause 3, wherein the preheating realizes that the heat exchanger is in the future by heat exchanger
The unbated reactor effluent from the two or more reactors is transferred to from the heat of the separation of (d).
5. according to the method described in any one of aforementioned clause, wherein at least one reactor includes key component
With 4 to 9 carbon atom number (i.e. C4-C9) hydrocarbon solvent mixture.
6. according to the method described in any one of aforementioned clause, wherein optional one or more comonomer packets in (b)
Containing ethylene, propylene, butylene, amylene, hexene, heptene, octene is one or more in decene or laurylene.
7. according to the method described in any one of aforementioned clause, wherein one in the two or more reactors
It polymerize homopolymer or random copolymer, and a polymerized copolymers in wherein described at least two or more the reactor.
8. according to the method described in clause 7, wherein the homopolymer is selected from：Isotactic polypropylene, syndiotactic poly- third
Alkene, atactic polypropylene, polyethylene, polybutene, polybutadiene, polypenthylene, polyhexene, poly- heptene, polyoctenamer, poly decene and
Polystyrene.
9. the method according to clause 7 or 8, wherein the copolymer is selected from ethylene-propylene copolymer, propylene-fourth
- 1 copolymer of alkene, -1 copolymer of propylene pentene-1, -1 copolymer of butene-hexene, -1 copolymer of propylene-heptene, propylene-octene -1
Copolymer, -1 copolymer of propylene-decene, -1 copolymer of Ethylene/Butylene, -1 copolymer of ethylene-pentene, polyethylene-hexene -1 are copolymerized
Object, -1 copolymer of ethylene-heptene, -1 copolymer of ethylene-octene.
10. according to the method described in clause 9, wherein incorporating one or more copolymers.
11. according to the method described in any one of aforementioned clause, further comprise the poor polymerization from the separation of (d)
Separate low molecular weight oligomers, low-molecular weight polymer, solvents/diluents or combination thereof in object vapor phase.
12. according to the method described in any one of aforementioned clause, wherein another by mixer and by what is then arranged
Outer low pressure separator realization merges rich in polymers liquid flow in step (f).
13. according to the method described in clause 12, accordingly, the rich in polymers liquid flow of step (e) before the combining, close
It is heated among and or after merging.
14. according to the method described in any one of aforementioned clause, it is anti-that wherein one or more described reactors are selected from tubular type
Answer the group of device, stirred tank, autoclave reactor, circulation flow reactor or combination thereof.
15. according to the method described in any one of aforementioned clause, wherein the low pressure separator preferably smaller than 1.5MPa,
More preferably less than under the pressure of 1.2MPa and more preferably less than 1.0MPa and preferably smaller than 240 DEG C, more preferably less than 220 DEG C simultaneously
And it is operated at a temperature of more preferably less than 200 DEG C.
16. according to the method described in any one of aforementioned clause, wherein the reactor preferably at least 120 DEG C, it is more excellent
At a temperature of at least 140 DEG C and most preferably at least 150 DEG C of choosing and preferably at least 5.0MPa, more preferably at least 6.0MPa and most
Preferably at least operated under the pressure of 7.0MPa.
17. according to the method described in any one of aforementioned clause, wherein relative to each other, at least two reactor
Volume ratio in the range of 0.85/1.0 and 1.0/0.85.
18. according to the method described in clause 4, wherein the preheating realizes that the heat exchanger is in the future by heat exchanger
The unbated reactor effluent from the two or more reactors is transferred to from the heat of the separation of (d)
Stream, therefore cooling stream in the heat exchanger at least partly condenses.
19. according to the method described in clause 4, coolant is the steaming from one or more low pressure separators accordingly
Gas.
20. according to the method described in clause 18,19 or 4, wherein the final heating period includes will be described unbated
Reactor effluent stream is heated to preferably at least 180 DEG C, more preferably at least 200 DEG C and most preferably at least 210 DEG C.
21. according to the method described in any one of aforementioned clause, wherein the poor polymer vapor stream is via recovery line
(5,11) are back to corresponding reactor.
Embodiment
Computer simulation is carried out using 8.8 computer softwares of Aspen.In this simulation, in flash separator (solution-air point
From device) in detached the solution taken out from the stage of reaction in embodiment E1, the solution contain 21.2wt% ethylene and 1- it is pungent
The copolymer of alkene, the n-hexane solvent of the unreacted vinyl monomer of 0.9wt% and 77.9wt% and unreacted 1- octenes
Comonomer.Accordingly, it is assumed that the temperature of solution stream is 220 DEG C before entering flash separator, it is assumed that into flash separation
Pressure is 90 bars before device, is 9 bars in flash separator.In comparative example CE2, detached in liquid liquid separator.According to
This, it is assumed that the temperature of solution stream is 220 DEG C before entering liquid liquid separator, and assumes that the pressure in liquid liquid separator is
30-45 bars.The comparison of technological process is shown in table 1.
Table 1
| E1 | CE2 | |
| It flows at top | Steam | Liquid |
| The amount of solution stream in the stream of top | 67.5wt% | 46wt% |
| The amount of polymer in the stream of top | 0wt% | 0.1wt% |
| The amount of ethylene in the stream of top | 1.4wt% | 1.9wt% |
| The amount of solvent+comonomer in the stream of top | 98.6wt% | 98.0wt% |
| It flows bottom | Liquid | Liquid |
| The amount of solution stream | 32.5wt% | 54wt% |
| The amount of polymer in the stream of bottom | 65wt% | 40wt% |
| The amount of ethylene in the stream of bottom | 0wt% | 0wt% |
| The amount of solvent+comonomer in the stream of bottom | 35wt% | 60wt% |
By comparing as can be seen that relative to liquid-liquid separation, flash separation is more effective, during this can be flowed by bottom
Find out compared with high polymer concentration.Relative to 54wt%, in E1 the liquid bottom stream of the 32.5wt% from solution stream total amount compared with
Low amounts allows further to concentrate using smaller downstream separator and isolating polymer.
Claims (15)
1. a kind of online blend method for polymer, including：
(a) two or more are provided and is in parellel arranged reactor-low pressure separator unit (1,7), each reactor-is low
Pressure separator unit is comprising a reactor (2,8) for being fluidly connected to a down stream low pressure separator (3,9) and further
The low pressure separator (3,9) connection is back to the recovery lines (5,11) of respective reaction device (2,8)；
(b) it is listed under making in the two or more reactors (2,8) of each reactor-low pressure separator unit (1,7)
Contact：
1) olefinic monomer with two or more carbon atoms,
2) one or more catalyst systems,
3) optional one or more comonomers,
4) optional one or more chain-transferring agents, and
5) optional one or more diluents or solvent,
The wherein described reactor (2,8) operates in the case where ensuring operating condition that reactor content forms single homogeneous phase, described
Reactor content includes the olefinic monomer, any existing comonomer, any existing diluent or solvent, Ren Hecun
Chain-transferring agent and polymeric articles；
The catalyst system for being used for each reactor accordingly includes one or more catalyst precarsors, one or more activation
Agent and optional one or more catalyst carriers；
(c) it includes not subtracting for homogeneous flow bulk polymer-monomer-solvent mixture to be formed in each reactor (2,8)
Few reactor effluent stream,
(d) make the unbated reactor effluent stream from each reactor (2,8) across corresponding low pressure point
From device (3,9),
The temperature and pressure of the low pressure separator (3,9) is adjusted accordingly so that liquid phase and vapor phase is obtained, to generate richness
Polymeric liquid phase and poor polymer vapor phase, and
(e) in each low pressure separator (3,9) by the poor polymer vapor phase from the rich in polymers liquid phase
Separation is to form the poor polymer vapor stream of separation and the rich in polymers liquid flow of separation；
(f) merge the rich in polymers liquid flow from step (e) in other low pressure separator and/or mixer (13)
To generate combined rich in polymers liquid flow (16)；
(g) the poor polymer vapor stream from step (e) is introduced back into corresponding anti-via recovery line (5,11)
It answers in device (2,8).
2. according to the method described in claim 1, it includes the step for the unbated reactor effluent stream for heating (c)
Suddenly.
3. according to the method described in claim 2, it includes the unbated reactor stream for heating (c) in two stages
The step of effluent stream, described two stages include warm-up phase and final heating period.
4. according to the method described in claim 3, wherein, the preheating is realized by heat exchanger, the heat exchanger is in the future
The unbated reactor effluent from the two or more reactors is transferred to from the heat of the separation of (d)
On.
5. method according to claim 3 or 4, wherein the final heating period includes by the unbated reaction
Device effluent stream is heated to preferably at least 180 DEG C, more preferably at least 200 DEG C and most preferably at least 210 DEG C.
6. according to any method of the preceding claims, wherein at least one reactor includes key component
With 4 to 9 carbon atom numbers, i.e. C4-C9, hydrocarbon solvent mixture.
7. according to any method of the preceding claims, wherein optional one or more comonomer packets of (b)
Containing ethylene, propylene, butylene, amylene, hexene, heptene, octene is one or more in decene or laurylene.
8. according to any method of the preceding claims, wherein one in the two or more reactors
It polymerize homopolymer or random copolymer, and a polymerized copolymers in wherein described at least two or more the reactor.
9. according to the method described in claim 8, wherein, the homopolymer is selected from：Isotactic polypropylene, syndiotactic poly- third
Alkene, atactic polypropylene, polyethylene, polybutene, polybutadiene, polypenthylene, polyhexene, poly- heptene, polyoctenamer, poly decene and
Polystyrene.
10. method according to claim 8 or claim 9, wherein the copolymer is selected from ethylene-propylene copolymer, propylene-fourth
- 1 copolymer of alkene, -1 copolymer of propylene pentene-1, -1 copolymer of butene-hexene, -1 copolymer of propylene-heptene, propylene-octene -1
Copolymer, -1 copolymer of propylene-decene, -1 copolymer of Ethylene/Butylene, -1 copolymer of ethylene-pentene, polyethylene-hexene -1 are copolymerized
Object, -1 copolymer of ethylene-heptene, -1 copolymer of ethylene-octene.
11. according to any method of the preceding claims, further comprising from the poor of the separation of step (d)
Separate low molecular weight oligomers, low-molecular weight polymer, solvents/diluents or combination thereof in polymer vapor phase.
12. according to any method of the preceding claims, wherein another by mixer and by what is then arranged
Outer low pressure separator, which is realized, merges the rich in polymers liquid flow in step (f).
13. according to any method of the preceding claims, wherein the rich in polymers liquid flow of step (e) exists
Before merging, merge among or merge after heated.
14. according to any method of the preceding claims, wherein the low pressure separator preferably smaller than 1.5MPa,
More preferably less than under the pressure of 1.2MPa and more preferably less than 1.0MPa and preferably smaller than 240 DEG C, more preferably less than 220 DEG C simultaneously
And it is operated at a temperature of more preferably less than 200 DEG C.
15. according to any method of the preceding claims, wherein the rich in polymers liquid phase based on the separation
Total weight content, it is by weight to come from the polymer content in the rich in polymers liquid phase of the separation of step (e)
40% to 90%.
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| EP15003632 | 2015-12-21 | ||
| EP15003632.5 | 2015-12-21 | ||
| PCT/EP2016/082184 WO2017108951A1 (en) | 2015-12-21 | 2016-12-21 | In-line blending process |
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| CN108473601A true CN108473601A (en) | 2018-08-31 |
| CN108473601B CN108473601B (en) | 2020-08-04 |
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| CN201680074936.6A Active CN108473601B (en) | 2015-12-21 | 2016-12-21 | In-line blending process |
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| US (1) | US10597472B2 (en) |
| EP (1) | EP3394112A1 (en) |
| KR (1) | KR102033267B1 (en) |
| CN (1) | CN108473601B (en) |
| BR (1) | BR112018012872B1 (en) |
| CA (1) | CA3005940C (en) |
| SA (1) | SA518391799B1 (en) |
| SG (1) | SG11201804142QA (en) |
| WO (1) | WO2017108951A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113329799A (en) * | 2019-01-25 | 2021-08-31 | 博里利斯股份公司 | Separation device and method for separating volatile compounds from a polymer reaction mixture |
| CN114425286A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Olefin hydration reaction system and olefin hydration method |
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|---|---|---|---|---|
| WO2019086987A1 (en) * | 2017-11-06 | 2019-05-09 | Nova Chemicals (International) S.A. | Polyolefin preparation process |
| US20220089802A1 (en) | 2019-01-28 | 2022-03-24 | Borealis Ag | Process for producing a polymer composition |
| WO2020156989A1 (en) | 2019-01-28 | 2020-08-06 | Borealis Ag | Polymer composition |
| JP7150200B2 (en) * | 2019-05-29 | 2022-10-07 | バーゼル・ポリオレフィン・ゲーエムベーハー | Suspension process for the production of ethylene polymers including workup of suspension medium |
| US20230250320A1 (en) | 2020-07-13 | 2023-08-10 | Borealis Ag | Adhesive polyethylene composition |
| EP4179036A1 (en) | 2020-07-13 | 2023-05-17 | Borealis AG | Adhesive polyethylene composition |
| KR20230079206A (en) * | 2020-09-30 | 2023-06-05 | 보레알리스 아게 | Plant and method for the production of in-line blended polymers |
| WO2022069410A1 (en) | 2020-09-30 | 2022-04-07 | Borealis Ag | Ethylene copolymers with improved melting and glass transition temperature |
| MX2023003542A (en) | 2020-09-30 | 2023-04-21 | Borealis Ag | Ethylene copolymers with improved melting and glass transition temperature. |
| EP4259666A1 (en) | 2020-12-08 | 2023-10-18 | Borealis AG | Polymerization process and arrangement |
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- 2016-12-21 BR BR112018012872-4A patent/BR112018012872B1/en active IP Right Grant
- 2016-12-21 US US15/776,095 patent/US10597472B2/en active Active
- 2016-12-21 KR KR1020187016534A patent/KR102033267B1/en active IP Right Grant
- 2016-12-21 SG SG11201804142QA patent/SG11201804142QA/en unknown
- 2016-12-21 WO PCT/EP2016/082184 patent/WO2017108951A1/en active Application Filing
- 2016-12-21 CA CA3005940A patent/CA3005940C/en active Active
- 2016-12-21 EP EP16815862.4A patent/EP3394112A1/en active Pending
- 2016-12-21 CN CN201680074936.6A patent/CN108473601B/en active Active
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| CN114425286B (en) * | 2020-10-29 | 2023-10-10 | 中国石油化工股份有限公司 | Olefin hydration reaction system and olefin hydration method |
Also Published As
| Publication number | Publication date |
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| CN108473601B (en) | 2020-08-04 |
| BR112018012872B1 (en) | 2022-07-26 |
| BR112018012872A2 (en) | 2018-12-04 |
| US20180327529A1 (en) | 2018-11-15 |
| KR102033267B1 (en) | 2019-10-16 |
| US10597472B2 (en) | 2020-03-24 |
| CA3005940C (en) | 2020-04-28 |
| WO2017108951A1 (en) | 2017-06-29 |
| KR20180085744A (en) | 2018-07-27 |
| SA518391799B1 (en) | 2021-09-21 |
| SG11201804142QA (en) | 2018-07-30 |
| CA3005940A1 (en) | 2017-06-29 |
| EP3394112A1 (en) | 2018-10-31 |
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